EP0870773B1 - Procédé de polymérisation d'éthylène en présence d'ecatalyseur à base d'oxyde de chrome - Google Patents

Procédé de polymérisation d'éthylène en présence d'ecatalyseur à base d'oxyde de chrome Download PDF

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Publication number
EP0870773B1
EP0870773B1 EP98302626A EP98302626A EP0870773B1 EP 0870773 B1 EP0870773 B1 EP 0870773B1 EP 98302626 A EP98302626 A EP 98302626A EP 98302626 A EP98302626 A EP 98302626A EP 0870773 B1 EP0870773 B1 EP 0870773B1
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EP
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Prior art keywords
catalyst
cycloalkane
polymerization
halogenated alkane
chromium
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Expired - Lifetime
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EP98302626A
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German (de)
English (en)
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EP0870773A1 (fr
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Daniel Bp Chemicals S.N.C. Maxant
Christian Bp Chemicals S.N.C. Philippart
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BP Chemicals SNC
BP Chemicals Ltd
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BP Chemicals SNC
BP Chemicals Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene

Definitions

  • the present invention relates to a process for the (co)polymerization of ethylene, optionally with one or more alpha-olefins, using a catalyst based on chromium oxide.
  • halogenated compounds are virulent poisons of catalysts based on chromium oxide in the polymerization of ethylene.
  • European Patent Application n° 0 186 174 discloses a process for (co-) polymerizing ethylene in the presence of a chromium oxide catalyst which is treated prior to or during the polymerization reaction by a modifying agent selected from carbon monoxides, carbonyl sulfide, hydrogen sulfide, oxygen, water, alcohols, aldehydes, ketones, mercaptans, amines and mixtures of any two or more thereof, under conditions so that to increase the environmental stress cracking resistance of the polymer produced.
  • Comparative run n° 28 discloses an ethylene/hexene-1 copolymerisation in suspension in liquid isobutane in the presence of a chromium oxide catalyst and carbon tetrachloride. The catalyst activity is reduced of about 10% in comparison to run 29 under identical conditions except for the presence of carbon tetrachloride.
  • United States Patent n°4, 194, 073 discloses an olefin polymerization process in the presence of a chromium oxide catalyst in a liquid hydrocarbon diluent, the catalyst being treated prior to or during the polymerization by an aromatic compound such as benzene, o-xylene, a monohalogenated derivative of benzene or o-xylene or mixtures thereof.
  • aromatic compound such as benzene, o-xylene, a monohalogenated derivative of benzene or o-xylene or mixtures thereof.
  • the presence of benzene tends to depress the catalyst activity during polymerization.
  • the present invention consequently relates to a process for a (co)polymerization of ethylene carried out in a gas phase polymerization medium in the presence of a catalyst based on chromium oxide, characterized in that the process comprises introducing into the said medium a halogenated alkane or cycloalkane in an amount such that the molar ratio of the halogenated alkane or cycloalkane to the chromium of the catalyst which are introduced into the gas phase polymerization medium is in a range from 0.001 to 1, preferably from 0.005 to 0.5, more particularly from 0.01 to 0.3.
  • the activity of the catalyst can be assessed and measured by the amount of (co)polymer manufactured per millimole of chromium per hour of reaction and per MPa of ethylene pressure and optionally of alpha-olefin pressure.
  • the activating effect of the halogenated alkane or cycloalkane is assessed, for its part, by comparing the activity of the catalyst in the presence and in the absence of the halogenated alkane or cycloalkane under (co)polymerization conditions which are moreover identical.
  • halogenated alkane or cycloalkane When a halogenated alkane or cycloalkane is used according to the present invention, it is surprisingly found a relatively large increase in the activity of the catalyst which is in general at least 10%. In most cases it may be greater than 15% and can reach e.g. 75%.
  • a monohalogenated or, preferably, polyhalogenated alkane or cycloalkane it is possible to use a monohalogenated or, preferably, polyhalogenated alkane or cycloalkane. It is preferable to use a monochlorinated or, preferably, polychlorinated alkane or cycloalkane.
  • the halogenated alkane can correspond to the general formula C n H a X b in which X represents a halogen atom, for example bromine or, preferably, chlorine, a and b are identical or different integers, a ranging from 0 to 2n + 1, preferably from 0 to 2n, b ranging from 1 to 2n + 2, preferably from 2 to 2n + 2, and the sum (a + b) being equal to 2n + 2.
  • n can range from 1 to 12 and b from 1 to 12
  • n can preferably range from 1 to 4 and b from 2 to 6, and more particularly n can be 1 or 2 and b range from 2 to 4.
  • the halogenated cycloalkane can correspond to the general formula C m H c X d in which X represents a halogen atom, for example bromine or, preferably, chlorine, c and d are identical or different integers, c ranging from 0 to 2m - 1, preferably from 0 to 2m - 2, d ranging from 1 to 2m, preferably from 2 to 2m, and the sum (c + d) being equal to 2m.
  • m can range from 5 to 12 and d from 1 to 12 and, preferably, m can range from 6 to 8 and d from 1 to 8.
  • Chloroform is preferred.
  • the present invention consequently also relates to a process for a (co)polymerization of ethylene carried out in a gas phase polymerization medium in the presence of a catalyst based on chromium oxide, characterized in that the process comprises introducing into the said medium a halogenated alkane or cycloalkane in an amount such that the molar ratio of the halogenated alkane or cycloalkane to the chromium of the catalyst which are introduced into the polymerization medium is in a range from 0.001 to 1, preferably from 0.005 to 0.5, more particularly from 0.01 to 0.3.
  • the (co)polymerization is carried out in a polymerization medium composed essentially of a gas phase, in particular in a fluidized-bed and/or mechanically stirred reactor.
  • the (co)polymerization can be carried out non-continuously or, preferably, continuously.
  • the ethylene and optionally the comonomer are introduced continuously into the gas phase polymerization medium, while the catalyst is introduced continuously or semi-continuously or intermittently into the gas phase polymerization medium and while the (co)polymer manufactured is withdrawn continuously or, preferably, semi-continuously or intermittently from the gas phase polymerization medium.
  • the halogenated alkane or cycloalkane is introduced continuously into the gas phase polymerization medium.
  • halogenated alkane or cycloalkane in the form of a solution or of a mixture in one or more liquid hydrocarbons, in particular C 4 to C 10 hydrocarbons, for example one or more C 4 to C 10 alkanes or cycloalkanes, such as n-pentane, isopentane, n-hexane or n-heptane.
  • the (co)polymerization can be carried out by introduction into the gas phase polymerization medium of specific additives, such as agents for modifying the (co)polymers of ethylene or for purifying the polymerization mixture, for example hydrogen, oxygen or organometallic compounds, such as organoaluminium compounds or organomagnesium compounds.
  • specific additives such as agents for modifying the (co)polymers of ethylene or for purifying the polymerization mixture, for example hydrogen, oxygen or organometallic compounds, such as organoaluminium compounds or organomagnesium compounds.
  • the process of the present invention makes it possible to polymerize ethylene alone or to copolymerize ethylene with at least one alpha-olefin, in particular a C 3 to C 8 alpha-olefin, such as propylene, 1-butene, 1-pentene, 1-hexene or 4-methyl- 1-pentene.
  • alpha-olefin in particular a C 3 to C 8 alpha-olefin, such as propylene, 1-butene, 1-pentene, 1-hexene or 4-methyl- 1-pentene.
  • the (co)polymerization can be carried out at a temperature of less than the melting point of the (co)polymer manufactured, generally at a temperature ranging from 30 to 120°C, preferably from 60 to 110°C, and under a total absolute pressure ranging from 0.1 to 5 MPa, preferably from 0.5 to 3 MPa.
  • the present invention advantageously relates to a continuous process for a gas phase (co)polymerization of ethylene with optionally at least one alpha-olefin, carried out in a fluidized-bed and/or mechanically stirred reactor, comprising the continuous introduction of ethylene and optionally of the alpha-olefin, the continuous or semi-continuous introduction of a catalyst based on chromium oxide and the continuous or semi-continuous withdrawal of the (co)polymer from the reactor, which process is characterized in that a halogenated alkane or cycloalkane is continuously introduced into the reactor in an amount such that the molar ratio of the halogenated alkane or cycloalkane to the chromium of the catalyst which are introduced into the reactor is in a range from 0.001 to 1, preferably from 0.005 to 0.5, more particularly from 0.01 to 0.3.
  • a gaseous polymerization medium which advantageously contains ethylene and optionally at least one alpha-olefin, hydrogen and an inert gas, such as nitrogen or a C 1 to C 8 alkane, preferably a C 4 to C 6 alkane, in particular isopentane and/or n-pentane, can circulate through the reactor.
  • an inert gas such as nitrogen or a C 1 to C 8 alkane, preferably a C 4 to C 6 alkane, in particular isopentane and/or n-pentane
  • an organometallic compound in particular an organoaluminium compound, such as triethylaluminium, into the reactor.
  • the (co)polymerization can also be carried out according to the process described in Patent Application PCT No. WO 94/28032.
  • the catalyst can also be used in the form of an ethylene prepolymer prepared outside the reactor prior to the (co)polymerization.
  • a flow rate is constant if it does not vary by more than 5%, preferably by not more than 2%, and that a ratio of one quantity to another is constant if it does not vary by more than 10%, preferably by not more than 5%.
  • the ethylene, and optionally alpha-olefin, partial pressures and the total pressure of the gaseous polymerization medium can vary continually with time. It is found that it is thus possible to continuously manufacture a (co)polymer of ethylene which is constant and high in quality, that is to say with a greatly reduced residual catalyst content.
  • the catalysts based on chromium oxide are obtained by a large number of known processes, in particular by those according to which, in a first stage, a chromium compound, such as a chromium oxide generally of formula CrO 3 , or a chromium compound which can be converted by calcination into chromium oxide, such as, for example, a chromium nitrate or sulphate, an ammonium chromate, a chromium carbonate, acetate or acetylacetonate or a tert-butyl chromate, is combined with a granular support based on a refractory oxide, such as, for example, silica, alumina, zirconium oxide, thorium oxide, titanium oxide or mixtures or coprecipitates of two or more of these oxides.
  • a chromium compound such as a chromium oxide generally of formula CrO 3
  • the chromium compound thus combined with the granular support is subjected to a so-called activation operation by heat treatment at a temperature of at least 250°C and of at most the temperature at which the granular support begins to sinter; the temperature of the heat treatment is generally between 250 and 1200°C and preferably between 350 and 1000°C.
  • This heat treatment is carried out under a non-reducing atmosphere, preferably under an oxidizing atmosphere, generally composed of a gas mixture comprising oxygen, such as, for example, air.
  • the duration of the heat treatment can be between 5 minutes and 24 hours, preferably between 30 minutes and 15 hours, so that, at the end of this treatment, the chromium compound is found to be at least partially in the hexavalent state.
  • the content by weight of chromium in the catalyst thus obtained is generally between 0.05 and 30% and preferably between 0.1 and 3%.
  • the granular supports based on a refractory oxide used in the preparation of the catalysts based on chromium oxide are generally provided in the form of solid particles which have a mean diameter by mass of between 20 and 300 ⁇ m.
  • These granular supports can be obtained by various known processes, in particular by precipitation of silicon compounds, such as silica, from an alkali metal silicate solution or alternatively by coprecipitation of a gel or of a hydrogel of a refractory oxide from solutions comprising at least two compounds chosen from silicon, titanium, zirconium, thorium or aluminium compounds. Such processes are described in particular in United States Patents No. 4,053,436 and No. 4,101,722.
  • Another method for the preparation of the catalysts based on chromium oxide can consist, first of all, in preparing a silica and titanium oxide support by calcination of a titanium compound, such as titanium tetraisopropoxide, deposited on silica, at a temperature of between 500 and 900°C under a dry air atmosphere, in then impregnating the said support with a chromium compound, such as tert-butyl chromate, and in subjecting the product obtained to the so-called activation operation by heat treatment.
  • a titanium compound such as titanium tetraisopropoxide
  • this cogel is dried and then subjected to the so-called activation operation by heat treatment.
  • Another technique for the preparation of the catalysts based on chromium oxide can consist in carrying out the so-called activation operation in the presence of certain titanium compounds, such as titanium tetraisopropoxide, according to a method described, for example, in French Patent No. 2,134,743.
  • Another method for the preparation of the catalysts based on chromium oxide can consist in carrying out the so-called activation operation in the presence of fluorine compounds chosen from ammonium hexafluorotitanate, tetrafluoroborate and hexafluoro-silicate and optionally in the presence of a titanium compound chosen from titanium alkoxides, this method advantageously making it possible to increase the activity of these catalysts or to modify the properties of the polyethylenes produced.
  • United States Patent No. 3,130,188 describes a supported catalyst based on chromium oxide, this catalyst being obtained in particular by the so-called activation operation in the presence of a fluorine compound, such as an ammonium fluorosilicate.
  • a fluorine compound such as an ammonium fluorosilicate.
  • 1,391,771 consists in carrying out the so-called activation operation for the supported catalyst based on chromium oxide in the presence, on the one hand, of a titanium compound, such as a titanium alkoxide, for example titanium tetraisopropoxide, and, on the other hand, of a fluorine compound, such as ammonium hexafluorotitanate, tetrafluoroborate or hexafluorosilicate.
  • a titanium compound such as a titanium alkoxide, for example titanium tetraisopropoxide
  • fluorine compound such as ammonium hexafluorotitanate, tetrafluoroborate or hexafluorosilicate.
  • the fluorine content in these catalysts is preferably between 0.05 and 8% by weight.
  • organometallic compounds such as an alteryl-aluminium alkoxide
  • the catalyst can contain from 0.05 to 30%, preferably from 0.1 to 3%, by weight of chromium and, moreover, from 0.1 to 20%, preferably from 1 to 10%, by weight of titanium and/or from 0.1 to 10%, preferably from 0.5 to 5%, by weight of aluminium and/or from 0.05 to 8%, preferably from 0.1 to 5%, by weight of fluorine.
  • One of the advantages of the process according to the present invention is to increase the activity of the catalyst in polymerization, that is to say to produce a larger amount of (co)polymer for the same amount of catalyst used, without substantially modifying the physical properties of the (co)polymer, such as the density or the distribution of the molecular masses. It is observed that the use of halogenated alkane or cycloalkane according to the present invention can increase the melt flow index of the (co)polymer as measured under the standard ASTM-D-1238 (condition F, P or E), that is to say decrease the weight-average molecular mass of the (co)polymer, which is often regarded as an advantage.
  • a catalyst based on chromium oxide supported on silica and modified with titanium was prepared in the following way.
  • a catalyst based on chromium (1% by weight of chromium) supported on silica, sold under the trade name "EP 30X” ® by Joseph Crossfield and Sons (Warrington GB) was introduced under a nitrogen atmosphere into a fluidized-bed activator. The activator was then heated to 150°C under nitrogen and was maintained at this temperature for 1.5 hours.
  • a mixture of titanium tetraisopropoxide and of titanium tetrabutoxide (in a molar ratio 80:20 respectively) was then introduced therein and the temperature was increased to 300°C.
  • the nitrogen was replaced with dry air and the temperature was raised to 550°C and then maintained at this level for 6 hours.
  • the activator was cooled to room temperature (to 20°C) and the catalyst was then stored under nitrogen. It contained 4.7% by weight of titanium and 1% by weight of chromium.
  • the polymerization was carried out exactly as in Example 1, except for the fact that no chloroform was introduced.
  • Example 1 It was observed that the instantaneous activity of the catalyst at the point where 400 g of polyethylene were produced was equal to 14,700 g.mMCr -1 .h -1 .MPa -1 . The activity of the catalyst in Example 1 was thus 15% higher than that observed in Example 2 (comparative).
  • the polymerization was carried out exactly as in Example 1, except for the fact that the chloroform was used in amounts such that the molar ratio of the chloroform to the chromium of the catalyst was successively 0.17, 0.20, 0.23 and 0.26. It was observed that the instantaneous activity of the catalyst for 400 g of polyethylene produced was respectively equal to 17,200, 19,200, 14,750 and 13,300 g.mMCr -1 .h -1 .MPa -1 .
  • the polymerization was carried out exactly as in Example 1, except for the fact that no TEA was introduced and that the amount of chloroform was such that the molar ratio of the chloroform to the chromium of the catalyst was 0.20. It was observed that the instantaneous activity of the catalyst for 400 g of polyethylene produced was equal to 7700 g.mMCr -1 .h -1 .MPa -1 .
  • Example 4 The polymerization was carried out exactly as in Example 4, except for the fact that no chloroform was used. It was observed that the instantaneous activity of the catalyst for 400 g of polyethylene produced was equal to 4400 g.mMCr -1 .h -1 .MPa -1 . The catalyst activity in Example 4 was 75% higher than that observed in Example 5 (comparative).
  • the polymerizations were carried out exactly as in Example 1, except for the fact that the catalyst used was the above-mentioned catalyst, and that the chloroform was used in amounts such that the molar ratio of the chloroform to the chromium of the catalyst was successively 0.04, 0.17, 0.20 and 0.23. It was observed that the instantaneous activity of the catalyst for 400 g of polyethylene produced was respectively equal to 17,960, 19,510, 18,980 and 15,110 g.mM Cr -1 .h -1 .MPa -1 .
  • the polymerization was carried out exactly as in Example 6, except for the fact that no chloroform was used.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Claims (9)

  1. Procédé de (co)polymérisation d'éthylène en présence d'un catalyseur à base d'oxyde de chrome, caractérisé en ce que le procédé est mis en oeuvre dans un milieu de polymérisation en phase gazeuse et comprend l'introduction dans ledit milieu d'un alcane ou d'un cycloalcane halogéné en une quantité telle que le rapport molaire de l'alcane ou du cycloalcane halogéné au chrome du catalyseur qui sont introduits dans le milieu de polymérisation en phase gazeuse est de 0,001 à 1.
  2. Procédé selon la revendication 1, caractérisé en ce. que l'alcane halogéné correspond à la formule générale CnHaXb dans laquelle X représente un atome d'halogène, a et b sont des nombres entiers identiques ou différents, a variant de 0 à 2n+1, b variant de 1 à 2n+2, et la somme (a+b) étant égale à 2n + 2, et dans lequel le cycloalcane halogéné correspond à la formule générale CmHcXd, dans laquelle X représente un atome d'halogène, c et d sont des nombres entiers identiques ou différents, c variant de 0 à 2m-1, d variant de 1 à 2m, et la somme (c+d ) étant égale à 2 m.
  3. Procédé selon l'une quelconque des revendications 1 à 2, caractérisé en ce que l'alcane ou le cycloalcane halogéné est choisi parmi le dichlorométhane, le chloroforme, le tétrachlorure de carbone, le 1,1,1-trichloroéthane ou le 1,2-dichloroéthane.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il est mis en oeuvre dans un réacteur à lit fluidisé et/ou à lit agité.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la (co)polymérisation est effectuée en continu et en ce que l'alcane ou le cycloalcane halogéné est introduit en continu dans le milieu de polymérisation en phase gazeuse.
  6. Procédé selon l'une quelconque des revendications 1 à 5 caractérisé en ce que l'alcane ou le cycloalcane halogéné est introduit sous la forme d'une solution ou d'un mélange dans un ou plusieurs hydrocarbures liquides.
  7. Procédé continu de (co)polymérisation en phase gazeuse d'éthylène avec éventuellement au moins une alpha-oléfine, mis en oeuvre dans un réacteur à lit fluidisé et/ou mécaniquement agité, comprenant l'introduction en continu de l'éthylène et éventuellement d'une alpha-oléfine, l'introduction continue ou semi-continue d'un catalyseur à base d'oxyde de chrome et le soutirage continu ou semi-continu du (co)polymère du réacteur, ledit procédé ayant pour caractéristique qu'un alcane ou cycloalcane halogéné est introduit en continu dans le réacteur en une quantité telle que le rapport molaire de l'alcane ou du cycloalcane halogéné au chrome du catalyseur qui sont introduits dans le réacteur soit de 0,001 à 1.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le catalyseur à base d'oxyde de chrome est modifié avec du titane et/ou de l'aluminium et/ou du fluor.
  9. Utilisation d'un alcane ou cycloalcane halogéné comme agent pour augmenter l'activité d'un catalyseur à base d'oxyde de chrome dans une (co)polymérisation en phase gazeuse d'éthylène.
EP98302626A 1997-04-10 1998-04-03 Procédé de polymérisation d'éthylène en présence d'ecatalyseur à base d'oxyde de chrome Expired - Lifetime EP0870773B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9704640 1997-04-10
FR9704640A FR2761998B1 (fr) 1997-04-10 1997-04-10 Procede de (co-) polymerisation de l'ethylene en presence de catalyseur a base d'oxyde de chrome

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EP0870773A1 EP0870773A1 (fr) 1998-10-14
EP0870773B1 true EP0870773B1 (fr) 2003-01-08

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EP (1) EP0870773B1 (fr)
CN (1) CN1197801A (fr)
AT (1) ATE230765T1 (fr)
DE (1) DE69810530T2 (fr)
DK (1) DK0870773T3 (fr)
ES (1) ES2191253T3 (fr)
FR (1) FR2761998B1 (fr)
ID (1) ID20153A (fr)
MY (1) MY116724A (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7915357B2 (en) 2005-07-27 2011-03-29 Univation Technologies, Llc Blow molding polyethylene resins

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905148B1 (fr) * 1997-09-27 2003-02-05 ATOFINA Research Catalyseurs pour la fabrication de polyéthylène et leur utilisation
EP1020481A1 (fr) * 1999-01-18 2000-07-19 Fina Research S.A. Production d'éthyléne
EP1207170A1 (fr) † 2000-11-20 2002-05-22 BP Chemicals S.N.C. Procédé de (co-)polymérisation continu des oléfines en phase gazeuse dans un réacteur en lit fluidisé
US6660817B2 (en) * 2001-07-24 2003-12-09 Eastman Chemical Company Process for the polymerization of ethylene and interpolymers thereof
US6646073B2 (en) * 2001-07-24 2003-11-11 Eastman Chemical Company Process for the polymerization of ethylene and interpolymers thereof
US6759492B2 (en) 2001-07-24 2004-07-06 Eastman Chemical Company Process for the polymerization of ethylene and interpolymers thereof
US6635726B2 (en) 2001-07-24 2003-10-21 Eastman Chemical Company Process for the polymerization of ethylene and interpolymers thereof
US8129484B2 (en) 2005-07-27 2012-03-06 Univation Technologies, Llc Blow molding polyethylene resins

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4194073A (en) * 1978-01-04 1980-03-18 Phillips Petroleum Company Olefin polymerization
CA1262009A (fr) * 1984-12-24 1989-09-26 John P. Hogan Methode de polymerisation pour la preparation d'homopolymeres et de copolymeres d'ethylene; produits ainsi obtenus

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7915357B2 (en) 2005-07-27 2011-03-29 Univation Technologies, Llc Blow molding polyethylene resins

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ID20153A (id) 1998-10-15
ATE230765T1 (de) 2003-01-15
FR2761998A1 (fr) 1998-10-16
ES2191253T3 (es) 2003-09-01
DK0870773T3 (da) 2003-05-05
DE69810530T2 (de) 2003-11-06
EP0870773A1 (fr) 1998-10-14
MY116724A (en) 2004-03-31
DE69810530D1 (de) 2003-02-13
FR2761998B1 (fr) 1999-06-04
CN1197801A (zh) 1998-11-04

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